CN115852733B - Carbon fiber paper for fuel cell gas diffusion layer and preparation method thereof - Google Patents
Carbon fiber paper for fuel cell gas diffusion layer and preparation method thereof Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 110
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 110
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000000446 fuel Substances 0.000 title claims abstract description 25
- 238000009792 diffusion process Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 27
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 polypropylene Polymers 0.000 claims abstract description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 20
- 239000011302 mesophase pitch Substances 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000004743 Polypropylene Substances 0.000 claims abstract description 14
- 229920001155 polypropylene Polymers 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 39
- 238000003763 carbonization Methods 0.000 claims description 38
- 238000004132 cross linking Methods 0.000 claims description 35
- 238000005087 graphitization Methods 0.000 claims description 35
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 31
- 238000005096 rolling process Methods 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 23
- 238000005507 spraying Methods 0.000 claims description 20
- 230000009471 action Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- MATSKSZAPIUFCB-UHFFFAOYSA-N 2,3-bis(ethenyl)phenol Chemical compound OC1=CC=CC(C=C)=C1C=C MATSKSZAPIUFCB-UHFFFAOYSA-N 0.000 claims description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- NBZANZVJRKXVBH-GYDPHNCVSA-N alpha-Cryptoxanthin Natural products O[C@H]1CC(C)(C)C(/C=C/C(=C\C=C\C(=C/C=C/C=C(\C=C\C=C(/C=C/[C@H]2C(C)=CCCC2(C)C)\C)/C)\C)/C)=C(C)C1 NBZANZVJRKXVBH-GYDPHNCVSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 abstract description 8
- 238000005452 bending Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 20
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000010000 carbonizing Methods 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 230000007480 spreading Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012753 anti-shrinkage agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a carbon fiber paper for a fuel cell gas diffusion layer and a preparation method thereof, and the raw materials for preparing the carbon fiber paper comprise: carbon fiber, vinylphenol, benzaldehyde, ammonia water, vinyl auxiliary cross-linking agent, soluble mesophase pitch and polypropylene powder, and the density of the obtained carbon fiber paper can be controlled at 0.36g/cm 3 The porosity can reach 80%, the bending strength can reach 43MPa, the thickness can be controlled to be 100-500um, the surface roughness can be controlled to be 6um, the resistivity can reach 4.5mΩ & cm (in-plane), and the heat conductivity can reach 22W/mK (25 ℃).
Description
Technical Field
The invention relates to the technical field of carbon fiber paper for a gas diffusion layer of a fuel cell, in particular to carbon fiber paper for a gas diffusion layer of a fuel cell and a preparation method thereof.
Background
Carbon fiber paper is applied to a gas diffusion layer for a fuel cell in its uniform porous structure and excellent gas permeability, low resistivity and high mechanical strength, high chemical stability and heat resistance, and has been developed rapidly in recent years, in particular, to a boost fuel cell.
The manufacturers of carbon fiber paper for fuel cell gas diffusion layers for automobiles having excellent performance at present mainly include foreign companies such as eastern japan, SGL germany, and Ballard, canada. The main preparation process of the carbon fiber paper comprises the following steps: the method comprises the steps of preparing base paper by a chopped carbon fiber-papermaking method, impregnating resin, pressing and forming, carbonizing at high temperature and graphitizing carbon fiber paper. The preparation process mainly has the following problems: (1) In the preparation process, carbon fibers are mainly dispersed in water, so that pollution problems exist; (2) In the process of impregnating resin, in order to improve the impregnation efficiency, solvents such as alcohol and the like are often required to be added to reduce the viscosity of resin glue solution, and a drying method is adopted to remove the solvents after impregnation, so that the pollution problem is also caused, the preparation time is also increased by drying, and the production efficiency is reduced; (3) The resin is impregnated and then is subjected to compression curing molding, so that intermittent preparation is realized, curing is performed for a plurality of hours, high energy consumption and long time consumption are realized, and the efficiency is low; (4) In the high-temperature carbonization and graphitization processes, the carbon residue is low after the carbonization of the conventional phenolic resin, the mechanical property is low, in addition, the carbon is not easy to be converted into graphitized carbon, and the prepared carbon fiber paper is low in conductivity. The problems of pollution caused by water dispersion, solvent pollution caused by high viscosity and solvent adding, low efficiency and high energy consumption caused by long pressing time at high temperature, poor mechanical property and low conductivity caused by low carbon residue and low graphitization rate and the like are to be solved.
There are also methods of preparing carbon fiber paper for a gas diffusion layer of a fuel cell by other means in the prior art, but a large amount of electrolyte is used, which causes a large amount of pollution. The formaldehyde solution is also adopted, but the preparation method is easy to volatilize and pollute the environment, and the prior art also has the problems of low carbon residue rate, poor heat shrinkage performance and the like.
Disclosure of Invention
The invention aims to overcome the defects of the existing materials and preparation methods and provide the carbon fiber paper for the fuel cell gas diffusion layer, which has the advantages of uniform pore, excellent air permeability, low resistivity, high mechanical strength, good chemical stability, excellent heat resistance and simple and rapid preparation process.
Another object of the present invention is to provide a method for preparing carbon fiber paper for a gas diffusion layer of a fuel cell having a novel resin structure and being rapidly cured and molded.
The technical scheme adopted by the invention is as follows:
the carbon fiber paper for the fuel cell gas diffusion layer comprises the following raw materials in parts by weight:
100 parts of carbon fiber
10-30 parts of vinyl phenol
10-30 parts of benzaldehyde
0.4 to 1.2 parts of ammonia water
1-3 parts of vinyl auxiliary cross-linking agent
5-10 parts of soluble mesophase pitch
3-5 parts of polypropylene powder.
The soluble mesophase pitch is a mixture composed of a plurality of flat disc-shaped polycyclic aromatic hydrocarbons, and the relative molecular mass of the soluble mesophase pitch is 370-2000.
The particle size of the polypropylene powder is 1-3 microns.
The carbon fiber is PAN-level carbon fiber yarn with the surface treated by vinyl silane, the diameter of the carbon fiber yarn is 7-7.5um, the carbon fiber yarn is cut into the length of 3-5cm, and then the carbon fiber yarn is formed into a carbon fiber paper preform through the action of air flow and the adhesive bonding action.
The vinyl phenol is one or more of para-vinyl phenol, ortho-vinyl phenol, divinyl phenol or trivinyl phenol;
the mass concentration of the ammonia water is 10-100%;
the vinyl auxiliary crosslinking agent is a monoethylene low molecular compound containing vinyl bonds, a divinyl crosslinking agent or a polyvinyl crosslinking agent.
The ammonia initiates the polycondensation reaction of vinyl phenol and formaldehyde under the action of irradiation crosslinking heat, and plays a role of an initiator.
Wherein the monoethylenically low molecular weight compounds include, but are not limited to, acrylic acid, hydroxypropyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, N-methylolacrylamide, hydroxyethyl acrylate, hydroxypropyl methacrylate, methacrylic acid, styrene or diacetone acrylamide; divinyl crosslinkers include, but are not limited to, divinylbenzene, tripropylene glycol dipropylene ether ester, 1, 4-butanediol diacrylate; the polyvinyl cross-linking agents include, but are not limited to, trivinylbenzene, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate, isovaleryltetraacrylate, or pentaerythritol tetraacrylate;
when the vinyl crosslinking agent can play a role in promoting crosslinking, the vinyl crosslinking agent can carry out a co-crosslinking reaction with vinyl phenol under the action of energy initiated by irradiation to form an irradiated vinyl crosslinking network. The irradiation vinyl cross-linked network and the phenolic resin cross-linked network form a cross-linked network, so that the distance between benzene ring structures in the whole large cross-linked network is shortened, high carbon residue is formed in the high-temperature carbonization and graphitization processes, and the strength of the carbon fiber/carbon material is improved.
The soluble mesophase pitch can form a large amount of carbon residues in the high-temperature carbonization and graphitization processes, the carbon residues can be converted into carbon with a graphite structure, and the resistance of the carbon fiber paper is reduced, so that the conductivity of the carbon fiber paper is improved.
The polypropylene powder can prevent the phenolic resin from excessively shrinking after the reaction, and ensure zero shrinkage of a cured product, thereby ensuring the thickness and thickness uniformity of the finally prepared carbon paper.
The invention also aims to provide a method for preparing the carbon fiber paper for the fuel cell gas diffusion layer, which has the advantages of high production efficiency, simple operation, high strength, small resistance, good chemical stability, excellent heat resistance, small pollution and low energy consumption, namely high efficiency and low energy consumption.
A method for preparing carbon fiber paper for a gas diffusion layer of a fuel cell, the method comprising the steps of:
(1) Carbon fiber cutting-resin spraying paper: cutting continuous carbon fibers into 3-5cm chopped carbon fibers, spraying a resin system consisting of vinylphenol, benzaldehyde, ammonia water, a vinyl crosslinking agent, soluble mesophase pitch and polypropylene powder, wherein the spraying thickness is 100-500um;
(2) And (3) irradiation crosslinking: irradiating by electron beam; in the electron beam irradiation process, the irradiation voltage is 0.1-2MeV, the current is 0.1-10mA, and the irradiation time is 30S-5min;
(3) Rolling, heating and crosslinking: continuously preparing a multi-network cured product by a rolling and heating cross-linking process method, and forming a cured product with a certain thickness under the action of rolling and heating; the rolling time is 30min-60min, and the temperature is 160-200 ℃;
(4) High temperature carbonization and graphitization: quickly preparing carbon fiber paper through high-temperature carbonization and graphitization reaction; the temperature in the carbonization process is 400-700 ℃, the heating rate is 50-200 ℃/h, and vacuum is pumped in the carbonization process; the high-temperature carbonization temperature is 900-1500 ℃, the heating rate is 50-200 ℃/h, and vacuum is pumped in the carbonization process; the temperature of the graphitization process is 2000-3200 ℃, the heating rate is 50-200 ℃/h, and nitrogen is filled in the graphitization process for protection.
In the step (1), spraying and liquid-phase impregnating are directly carried out on the cut carbon fibers to form paper, so that the resin is fully contacted with the carbon fibers, and the carbon fibers are impregnated by utilizing a low-viscosity polymer precursor;
the invention does not need to add a diluting solvent, and the preparation process is more environment-friendly and pollution-free.
The whole preparation process does not need to add a metal catalyst, and the final product has high purity after carbonization.
The invention can quickly crosslink vinyl groups within five minutes to form a vinyl crosslinked network, improves the efficiency, reduces the energy consumption, and is one of the innovation points of the invention.
In addition, the invention uses vinyl phenol and formaldehyde with special structure to chain and initiate the crosslinking reaction, thereby greatly improving the reaction efficiency.
The thermal initiation of the phenolic condensation reaction by irradiation is another invention point of the present invention.
The rolling heating process in the step (3) is a continuous production process, the thickness of the product, namely thickness uniformity, can be ensured by rolling, and meanwhile, the crosslinking reaction can be promoted by heating, so that the reaction is ensured to be complete.
The continuous rolling production improves the production efficiency, ensures the uniformity of the product quality, and is one of the innovation points of the invention.
The carbon fiber paper (see the carbon fiber paper microcosmic chart of figure 2 in detail) has the following advantages:
(1) Low density and high porosity
The chopped carbon fibers are mutually stacked in the spraying process to form a porous network structure, the carbon fibers are bonded by a resin system, and the resin is carbonized into a porous bonding structure after high-temperature carbonization and graphitization, so that the carbon fiber paper has lower density and higher porosity, and the density of the carbon fiber paper can be controlled to be 0.35-0.45g/cm 3 The porosity can reach 80%.
(2) High strength
According to the invention, through the double-network crosslinking and grafting effect of the vinyl phenolic resin, the vinyl phenolic resin has high crosslinking density, the vinyl phenolic resin is tightly combined with the carbon fiber, the intermolecular distance is small, and meanwhile, through adding the high-carbon residue soluble mesophase pitch, the finally carbonized and graphitized material has higher mechanical property and high material strength, and is beneficial to operation and subsequent use. The bending strength can reach 43MPa.
(3) Uniform thickness and low surface roughness
The polypropylene powder in the resin formula system can ensure zero shrinkage in the reaction process, and the thickness of the cured composite material system is uniform and the surface is smooth by adding heating and rolling. In the carbonization and graphitization processes, the control effect of the graphite paper and the graphite blocks further ensures that the carbon fiber paper after carbonization and graphitization has uniform thickness and low surface roughness. The thickness of the material can be controlled between 100 and 500um, and the surface roughness is controlled to be 6um.
(4) Low resistivity and high thermal conductivity
The resin formula system is added with the soluble mesophase pitch with high carbon residue, so that the carbonized and graphitized carbon fiber has higher carbon residue, the high carbon residue connects the carbon fiber into a network whole, the resistivity is reduced, the heat conductivity is improved, and meanwhile, the carbon residue is converted into a graphite structure in the high-temperature graphitization process, the resistivity can be further reduced, the heat conductivity is improved, and the network whole of the carbon fiber paper has lower resistivity and higher heat conductivity. The resistivity of the carbon fiber paper can reach 4.5mΩ & cm (in-plane), and the thermal conductivity can reach 22W/mK (25 ℃ in-plane).
(5) Environmental protection
The preparation process adopts a micromolecular compound system, is easy to impregnate, solves the problem that the conventional resin is high in viscosity and difficult to impregnate, and has no solvent pollution in the reaction process, so that the preparation process is environment-friendly.
(6) High efficiency and low energy consumption
In the preparation process, the heat of the irradiation crosslinking polyethylene is used for initiating the phenolic aldehyde condensation reaction, heating curing is not needed, the energy consumption is low, in addition, the irradiation crosslinking initiation rate is high, and the vinyl crosslinking can be initiated within 5 minutes. The continuous operation is adopted in the rolling, heating and crosslinking process, so that the reaction rate can be quickened, and the product quality can be ensured.
The carbon fiber paper obtained by the invention can meet the severe performance requirements of the gas diffusion layer of the fuel cell by virtue of various excellent performances.
Drawings
FIG. 1 is a schematic illustration of a process for producing carbon fiber paper according to the present invention;
fig. 2 is an example of a microscopic morphology graph of the carbon fiber paper prepared by the present invention.
Detailed Description
The present invention will be described in further detail by way of examples. The present invention is not limited to the following examples.
Example 1
A preparation method of carbon fiber paper for a fuel cell gas diffusion layer comprises the following steps:
(1) Carbon fiber cutting-resin spraying paper: the continuous carbon fiber is cut into 3cm short carbon fiber under the action of a three-roller cutter, a resin system (comprising 10 parts of vinyl phenol, 15 parts of benzaldehyde, 1 part of ammonia water, 1 part of styrene, 5 parts of soluble mesophase pitch and 3 parts of polypropylene powder) is mixed and sprayed in a spray gun, the carbon fiber and the resin system are sprayed on release paper under the action of air flow, and the final mass ratio of the spraying liquid to the carbon fiber is 35:100, the thickness is controlled at 200um.
(2) And (3) irradiation crosslinking: spreading the sprayed and impregnated sample on a tray for irradiation to trigger vinyl crosslinking, and transmitting irradiation back and forth, wherein the type and working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time was 5min.
(3) Rolling, heating and crosslinking: the irradiated sample is conveyed to a roller press, the rolling temperature is 180 ℃, and the rolling time is 30min;
(4) High temperature carbonization and graphitization: and (3) placing the cured product into a graphite mold, fixing, carbonizing and graphitizing, clamping the cured product between 200-micrometer thick graphite paper, pressing the cured product by a graphite plate with the thickness of 2 centimeters, directly performing carbonization and graphitization reaction in a high-temperature furnace, wherein the carbonization and graphitization temperature is 400 ℃/3h+600 ℃/3h+700 ℃/2h+1200 ℃/1h+2500 ℃/2h, the heating rate is 100 ℃/h, the vacuum pressure is 10-8000Pa, and filling nitrogen for protection during graphitization at the temperature of 2500 ℃. And (5) cooling to normal temperature by water, taking out, weighing, and finally preparing the carbon fiber paper.
The density of the carbon fiber paper is 0.35g/cm 3 The porosity was 82% and the flexural strength was 41MPa. The thickness was 200um and the surface roughness was 6.3um. The resistivity of the carbon fiber paper can reach 5.0mΩ & cm (in-plane), and the thermal conductivity can reach 21W/mK (25 ℃), in-plane.
Example 2
A preparation method of carbon fiber paper for a fuel cell gas diffusion layer comprises the following steps:
(1) Carbon fiber cutting-resin spraying paper: the continuous carbon fiber is cut into 3cm short carbon fiber under the action of a three-roller cutter, a resin system (comprising 10 parts of vinyl phenol, 13 parts of benzaldehyde, 1 part of ammonia water, 1 part of tripropylene glycol dipropyl ether ester, 6 parts of soluble mesophase pitch and 4 parts of polypropylene powder) is mixed and sprayed in a spray gun, the carbon fiber and the resin system are sprayed on release paper under the action of air flow, and the final mass ratio of spray liquid to the carbon fiber is 35:100, the thickness is controlled at 300um.
(2) And (3) irradiation crosslinking: spreading the sprayed and impregnated sample on a tray for irradiation to trigger vinyl crosslinking, and transmitting irradiation back and forth, wherein the type and working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time was 5min.
(3) Rolling, heating and crosslinking: the irradiated sample is conveyed to a roller press, the rolling temperature is 180 ℃, and the rolling time is 30min;
(4) High temperature carbonization and graphitization: and (3) placing the cured product into a graphite mold, fixing, carbonizing and graphitizing, clamping the cured product between 200-micrometer thick graphite paper, pressing the cured product by a graphite plate with the thickness of 2 centimeters, placing the cured product into a high-temperature furnace, directly carrying out carbonization and graphitization reaction at the carbonization and graphitization temperature of 400 ℃/3h+600 ℃/3h+700 ℃/3h+1200 ℃/1h+2800 ℃/2h, heating the cured product at the heating rate of 100 ℃/h, and filling nitrogen for protection when graphitizing at the vacuum pressure of 10-8000Pa and the temperature of 2800 ℃. And (5) cooling to normal temperature by water, taking out, weighing, and finally preparing the carbon fiber paper.
The density of the carbon fiber paper is 0.36g/cm 3 The porosity was 80% and the flexural strength was 42MPa. The thickness was 300um and the surface roughness was 6.1um. The resistivity of the carbon fiber paper can reach 4.7mΩ & cm (in-plane), and the thermal conductivity can reach 21.5W/mK (25 ℃), in-plane.
Example 3
A preparation method of carbon fiber paper for a fuel cell gas diffusion layer comprises the following steps:
(1) Carbon fiber cutting-resin spraying paper: the continuous carbon fiber is cut into 3cm short carbon fiber under the action of a three-roller cutter, a resin system (comprising 10 parts of vinyl phenol, 10 parts of benzaldehyde, 1 part of ammonia water, 1 part of pentaerythritol tetraacrylate, 8 parts of soluble mesophase pitch and 5 parts of polypropylene powder) is mixed and sprayed in a spray gun, the carbon fiber and the resin system are sprayed on release paper under the action of air flow, and the final mass ratio of the spraying liquid to the carbon fiber is 35:100, the thickness is controlled at 400um.
(2) And (3) irradiation crosslinking: spreading the sprayed and impregnated sample on a tray for irradiation to trigger vinyl crosslinking, and transmitting irradiation back and forth, wherein the type and working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time was 5min.
(3) Rolling, heating and crosslinking: the irradiated sample is conveyed to a roller press, the rolling temperature is 180 ℃, and the rolling time is 30min;
(4) High temperature carbonization and graphitization: and (3) placing the cured product into a graphite mold, fixing, carbonizing and graphitizing, clamping the cured product between 200-micrometer thick graphite paper, pressing the cured product by a graphite plate with the thickness of 2 centimeters, directly performing carbonization and graphitization reaction in a high-temperature furnace, wherein the carbonization and graphitization temperature is 400 ℃/3h+600 ℃/3h+700 ℃/3h+1200 ℃/1h+3200 ℃/2h, the heating rate is 100 ℃/h, the vacuum pressure is between 10 Pa and 8000Pa, and filling nitrogen for protection during graphitization at the temperature of 3200 ℃. And (5) cooling to normal temperature by water, taking out, weighing, and finally preparing the carbon fiber paper.
The density of the carbon fiber paper can be controlled to be 0.36g/cm 3 The porosity can reach 80%. The bending strength can reach 43MPa. The thickness of the material can be controlled at 400um, and the surface roughness is controlled at 6um. The resistivity of the carbon fiber paper can reach 4.5mΩ & cm (in-plane), and the thermal conductivity can reach 22W/mK (25 ℃ in-plane).
Comparative example 1
(1) Carbon fiber cutting-resin spraying paper: the continuous carbon fiber is cut into 3cm short carbon fiber under the action of a three-roller cutter, a resin system (comprising 10 parts of vinyl phenol, 15 parts of benzaldehyde, 1 part of ammonia water and 1 part of styrene) is mixed and sprayed out in a spray gun, the carbon fiber and the resin system are sprayed on release paper under the action of air flow, and the final mass ratio of a spraying liquid to the carbon fiber is 27:100, the thickness is controlled at 200um.
(2) And (3) irradiation crosslinking: spreading the sprayed and impregnated sample on a tray for irradiation to trigger vinyl crosslinking, and transmitting irradiation back and forth, wherein the type and working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time was 5min.
(3) Rolling, heating and crosslinking: the irradiated sample is conveyed to a roller press, the rolling temperature is 180 ℃, and the rolling time is 30min;
(4) High temperature carbonization and graphitization: and (3) placing the cured product into a graphite mold, fixing, carbonizing and graphitizing, clamping the cured product between 200-micrometer thick graphite paper, pressing the cured product by a graphite plate with the thickness of 2 centimeters, directly performing carbonization and graphitization reaction in a high-temperature furnace, wherein the carbonization and graphitization temperature is 400 ℃/3h+600 ℃/3h+700 ℃/2h+1200 ℃/1h+2500 ℃/2h, the heating rate is 100 ℃/h, the vacuum pressure is 10-8000Pa, and filling nitrogen for protection during graphitization at the temperature of 2500 ℃. And (5) cooling to normal temperature by water, taking out, weighing, and finally preparing the carbon fiber paper.
The density of the carbon fiber paper is 0.36g/cm 3 The porosity was 80% and the flexural strength was 30MPa. The thickness was 190um and the surface roughness was 20um. The resistivity of the carbon fiber paper can reach 8.0mΩ & cm (in-plane), and the thermal conductivity can reach 15W/mK (25 ℃ in-plane). Because no anti-shrinkage agent polypropylene powder and high carbon residue soluble mesophase pitch are added, the thickness of the material is shrunk, the surface is uneven, the roughness is high, the strength is lower, the resistivity is higher, and the heat conductivity coefficient is lower.
Comparative example 2
(1) Carbon fiber cutting-resin spraying paper: the continuous carbon fiber is cut into 3cm short carbon fiber under the action of a three-roller cutter, a resin system (comprising 10 parts of phenol, 15 parts of benzaldehyde, 1 part of ammonia water and 1 part of hydroxyethyl acrylate) is mixed and sprayed out in a spray gun, the carbon fiber and the resin system are sprayed on release paper under the action of air flow, and the final mass ratio of a spraying liquid to the carbon fiber is 27:100, the thickness is controlled at 200um.
(2) And (3) irradiation crosslinking: spreading the sprayed and impregnated sample on a tray for irradiation to trigger vinyl crosslinking, and transmitting irradiation back and forth, wherein the type and working condition of the electron accelerator are GJ-2E-EB,2MeV and 10mA. The irradiation time was 5min.
The liquid resin system cannot be crosslinked under irradiation, the resin cannot be cured, a solid material cannot be prepared, and the sample preparation fails.
Claims (6)
1. The carbon fiber paper for the fuel cell gas diffusion layer is characterized by comprising the following raw materials in parts by weight:
100 parts of carbon fiber
10-30 parts of vinyl phenol
10-30 parts of benzaldehyde
0.4 to 1.2 parts of ammonia water
1-3 parts of vinyl auxiliary cross-linking agent
5-10 parts of soluble mesophase pitch
3-5 parts of polypropylene powder;
the preparation method of the carbon fiber paper for the fuel cell gas diffusion layer comprises the following steps:
(1) Carbon fiber cutting-resin spraying paper: cutting continuous carbon fibers into 3-5cm chopped carbon fibers, spraying a resin system consisting of vinyl phenol, benzaldehyde, ammonia water, a vinyl crosslinking agent, soluble mesophase pitch and polypropylene powder, wherein the spraying thickness is 100-500 mu m;
(2) And (3) irradiation crosslinking: irradiating by electron beam; in the electron beam irradiation process, the irradiation voltage is 0.1-2MeV, the current is 0.1-10mA, and the irradiation time is 30s-5min;
(3) Rolling, heating and crosslinking: continuously preparing a multi-network cured product by a rolling heating crosslinking process, and forming the cured product under the action of rolling heating; the rolling time is 30min-60min, and the temperature is 160-200 ℃;
(4) High temperature carbonization and graphitization: quickly preparing carbon fiber paper through high-temperature carbonization and graphitization reaction; the temperature in the carbonization process is 400-700 ℃, the heating rate is 50-200 ℃/h, and vacuum is pumped in the carbonization process; the high-temperature carbonization temperature is 900-1500 ℃, the heating rate is 50-200 ℃/h, and vacuum is pumped in the carbonization process; the temperature of the graphitization process is 2000-3200 ℃, the heating rate is 50-200 ℃/h, and nitrogen is filled in the graphitization process for protection.
2. The carbon fiber paper for a gas diffusion layer of a fuel cell according to claim 1, wherein the soluble mesophase pitch is a mixture of a plurality of kinds of flat disc-shaped polycyclic aromatic hydrocarbons having a relative molecular mass of 370 to 2000.
3. The carbon fiber paper for a fuel cell gas diffusion layer according to claim 1, wherein the polypropylene powder has a particle size of 1 to 3 μm.
4. The carbon fiber paper for a gas diffusion layer of a fuel cell according to claim 1, wherein the carbon fiber is a surface-treated PAN-grade carbon fiber yarn of a vinylsilane having a diameter of 7 to 7.5 μm, cut into a length of 3 to 5cm, and then formed into a carbon fiber paper preform by an air flow action and an adhesive bonding action.
5. The carbon fiber paper for a fuel cell gas diffusion layer according to claim 1, wherein the vinylphenol is one or more of para-vinylphenol, ortho-vinylphenol, divinylphenol, or trivinylphenol; the mass concentration of the ammonia water is 10-100%; the vinyl auxiliary crosslinking agent is a monoethylene low molecular compound containing vinyl bonds, a divinyl crosslinking agent or a polyvinyl crosslinking agent.
6. A method for producing carbon fiber paper for a gas diffusion layer of a fuel cell according to any one of claims 1 to 5, comprising the steps of:
(1) Carbon fiber cutting-resin spraying paper: cutting continuous carbon fibers into 3-5cm chopped carbon fibers, spraying a resin system consisting of vinyl phenol, benzaldehyde, ammonia water, a vinyl crosslinking agent, soluble mesophase pitch and polypropylene powder, wherein the spraying thickness is 100-500 mu m;
(2) And (3) irradiation crosslinking: irradiating by electron beam; in the electron beam irradiation process, the irradiation voltage is 0.1-2MeV, the current is 0.1-10mA, and the irradiation time is 30s-5min;
(3) Rolling, heating and crosslinking: continuously preparing a multi-network cured product by a rolling heating crosslinking process, and forming the cured product under the action of rolling heating; the rolling time is 30min-60min, and the temperature is 160-200 ℃;
(4) High temperature carbonization and graphitization: quickly preparing carbon fiber paper through high-temperature carbonization and graphitization reaction; the temperature in the carbonization process is 400-700 ℃, the heating rate is 50-200 ℃/h, and vacuum is pumped in the carbonization process; the high-temperature carbonization temperature is 900-1500 ℃, the heating rate is 50-200 ℃/h, and vacuum is pumped in the carbonization process; the temperature of the graphitization process is 2000-3200 ℃, the heating rate is 50-200 ℃/h, and nitrogen is filled in the graphitization process for protection.
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| KR20180023830A (en) * | 2016-08-25 | 2018-03-07 | 국일제지 주식회사 | A manufacturing method of carbon paper for fuel cell gas diffusion layers which adds pitch-based carbon fibers and aqueous binders, and carbon paper for the fuel cell gas diffusion layers using the same |
| CN108914681A (en) * | 2018-07-06 | 2018-11-30 | 天津工业大学 | A kind of preparation method of carbon fiber paper |
| CN113277868A (en) * | 2021-05-25 | 2021-08-20 | 杭州幄肯新材料科技有限公司 | Light carbon fiber/carbon composite thermal field material and preparation method thereof |
| CN113584940A (en) * | 2021-06-24 | 2021-11-02 | 浙江超探碳纤维科技有限公司 | Preparation method of carbon fiber paper |
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| KR20180023830A (en) * | 2016-08-25 | 2018-03-07 | 국일제지 주식회사 | A manufacturing method of carbon paper for fuel cell gas diffusion layers which adds pitch-based carbon fibers and aqueous binders, and carbon paper for the fuel cell gas diffusion layers using the same |
| CN108914681A (en) * | 2018-07-06 | 2018-11-30 | 天津工业大学 | A kind of preparation method of carbon fiber paper |
| CN113277868A (en) * | 2021-05-25 | 2021-08-20 | 杭州幄肯新材料科技有限公司 | Light carbon fiber/carbon composite thermal field material and preparation method thereof |
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